Photographic elements containing polymeric esters as ultraviolet absorbing compounds



2,8 75,053 0 ESTERS mas Feb. 24, 1959 M. MINSK v PHOTOGRAPHIC ELEMENTS CONTAINING POLYMERI AS ULTRAVIOLET ABSORBING COMPOU Filed May 26, 1955 DE 602 020 00. a NR P MOE MN /E5 0 WWW m 0R5 0% m 5 6 Wm M 0 0 P ULTRAVIOLET F/LTE/F LAYER WAVELENGTH (mp) Fig 3 Fig. 2 0

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6' a 400 ATTORNEYS WAVELENGTH/ml!) \ERsQQ violet radiation millimicrons.

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United States Patent PHOTOGRAPHIC ELEMEN'IS CONTAINING POLY- MERIC ESTERS AS ULTRAVIOLET ABSORBING COMPOUNDS Claims. (CI. 96-84) This invention relates to new products and new photographic elements protected against the harmful effects of ultraviolet radiation.

It is known that certain materials such as cellulosic films and photographic layers, are adversely affected by ultraviolet radiation when such materials are exposed to daylight. In the case of photographic layers, the ultra- .violet radiation sometimes causes undesiredexposure of the layer, or layers, since photographic silver halide emulsions are sensitive to blue, violet and ultraviolet regions of the spectrum, in addition to any other sensitivity which may be given them, and in the exposure of such material, it is frequently desirable to prevent the action of ultraviolet light on the sensitive emulsion. This is especially true in the case of photographic materials designed for use in color photography where the film has been sensitized to the longer wavelength regions where it is desirable to; record only the rays. of the visible spectrum.

Colorphotographs on multilayer photographic mate rial, particularly where the dye images are formed in sensitive emulsion layers by color development, are susceptible to fading and discoloration by the action of ultrato which the photographs are subjected during viewing. It is also known that the residual couplers contained in the emulsion layers after formation of the picture images in certain processes are attacked by ultra violet radiation and form a stain which is undesirable in the finished photograph. The action of ultraviolet radiation on finished color photographs is particularly noticeable in positive prints on paper or other opaque supports, since this type of print is frequently viewed in daylight where there is a high content of ultraviolet radiation. This dye fading and yellowing appears to be caused primarily by those wavelengths of light which lie close to the visual region of the spectrum, i. e., 260-400 I have now found that certain new ultraviolet absorbing compounds can be used to overcome the aforementioned difliculties without attendant harmful action by the ultraviolet absorbing compounds.

It is, therefore, an object of my invention to provide new compounds and methods of making these new compounds. Another object is to provide photographic elements protected against the harmful effects of ultraviolet radiation. A further object is to provide photographic color materials which have been protected against the harmful effects of ultraviolet radiation. Other objects will become apparent from a consideration of the following description and examples.

It is known in the art that the incorporation of a substance which selectively absorbs ultraviolet radiation prevents or reduces some of the disadvantages presented through the use of cellulosic films or photographic layers. However, the substances which have been previously incorporated to produce this desirable effect suffer from the disadvantage that they either (1) tend to leach or bleed from their films, and their eiiectiveness is thus (2) tendto separate or crystallize from their solid 2,815,053 Patented Feb. 24,

. 2 7 solutions, resulting in a hazy and sometimes brittle film.

These difiiculties are overcome in the instant invention by attaching a certain type of macromolecule to compounds which have the property of absorbing the undesirable ultraviolet radiation but have no substantial absorption in the visible region of the spectrum, i. e., from about 400-700 m Such a. combination helps toprevent diffusion and at the same time makes orientation of the molecule increasingly difiicult, thus reducing the danger of crystallization. Moreover, the customary vehicles employed in the photographic art have a greater compatibility for the polymeric ultraviolet absorbing compounds of my invention than for the non-polymeric compounds alone.

The polymeric ultraviolet absorbing compounds of my invention are represented by polymerized monoethylenically-unsaturated compounds having chemically attached thereto through an ester or an amide linkage a compound having its maximum absorption between 260- 400 m with no substantial absorption between 400- 700 III/4. Since the ultraviolet absorbing component is prepared, according to my invention, by .reaction with a polymerized monoethylenically-unsaturated compound containing reactive chemical groups, such as carboxylic anhydride or carboxylic halide (e. g., chloride, bromide,

etc.), it is apparent that the reaction need not be complete in order to obtain the advantages of my invention. That is, not all of the reactive anhydride or carboxylic halide groups in the polymerized compounds need undergo reaction. However, it is generally advantageous to have at least 10 percent of such reactive groups combined with the ultraviolet absorbing component.

According to my invention, I provide the new ultraviolet absorbing compounds by reacting an ultraviolet absorbing compound containing a hydroxyalkyl (e. g., B-hydroxyethyl, B-hydroxypropyl, -hydroxypropl, etc.), an aminoalkyl (e g., aminoethyl, aminopropyl,etc.) or an aminoaryl e. g., aminophenyl, aminotolyl, etc.) group with a linear synthetic polymer containing carboxylic halide or carboxylic anhydride groups;

As synthetic polymers useful in my invention, I can advantageously employ such polymers as the interpolymers of maleic anhydride, e. g., interpolymers of maleic anhydride with styrene, vinyl acetate, vinyl chloride,

alkylvinyl ethers (e. g., ethylvinyl ether, etc.), acrylic acid, a-methacrylic acid, etc., as well as the corresponding polymers of maleyl and fumaryl halides (e. g., chlorides, bromides, etc.) with these vinyl or vinylidene compounds; polyacrylyl halides (e. g., polyacrylyl chloride, polymethacrylyl chloride, etc.) polyacrylic anhydrides (e. g., polyacrylic anhydride, poly a-methacrylic anhydride, etc.); etc. The polymerized monoethylenically-unsaturated compounds or synthetic polymers of my invention are obtained from a polymeriz-able unsaturated compound containing a CH =C group, as can be seen from the resins listed above. Useful interpolymers of maleic anhydride, substituted maleic anhydrides (e. g., citraconic anhydride, phenyl maleic anhydride, etc.); fumaryl halides, maleyl halides with vinyl compounds are 'described in Voss et a1. U. S. Patent 2,047,398, dated July 14, 1936. Useful polymers of acrylic halides (i. e.,. acrylic halides and a-methacrylic halides) are described in' Marck et al. U. S. Patent 1,984,417, dated December 18, 1934. Such polymers include, for example, polyacrylyl chloride, polymethacrylyl chloride, as well as copolymers of these halides with a vinyl (or. vinylidene) compound, such as vinyl acetate, styrene, ethyl acrylate, acrylonitrile, etc,

The ultraviolet invention containing a hydroxyalkyl, aminoalkyl or aminoy group,

absorbing components used in my which are reacted with the synthetic polymers listed above, comprise a class of compounds having sub stantially no absorption of visible radiation, i. e., they are colorless, but having the property of absorbing substantial amounts of radiation shorter than 400 m The hydroxyalkyl, aminoallryl or aminoaryl groups required in the ultravioletabsorbing component can be attached to the molecule through'a carbon linkage, or this group canbe attached through some other linkage such as an ether linkage '(e. g., ,B-hydroxyethoxy, etc.). Among the ultravioletabsorbing components which can be reacted with the synthetic resins listed above are those represented by the following general formulas:

wherein R and R each represents an alkyl group (e. g., methyl, ethyl, etc.) or an aryl group (e. g., phenyl, mand p-tolyl, 0-, mand p-methoxyphenyl, etc.), R and R each represents an aryl group (e. g., phenyl, o-, mand p-tolyl, etc.), R represents an aryl group (e. g.,

phenyl, o-, mand p-tolyl, p-(B-hydroxyethoxy)phenyl,

m-(p-ethoxy)phenyl, p-(B-hydroxyethyDphenyl, etc.), R represents an alkyl group (e. g., methyl, ethyl, etc.) or an aryl group (e. g., such as thoselisted above for R (provided that at least R or R contains a hydroxyalkyl radical), and R represents an aminoaryl group (e. g., o-, 'mand p-aminophenyl, etc.). I

The intermediates represented by Formula I above can advantageously be prepared by condensing together a hydrazine compound selected from those represented by the following general formula: (VI) IIQNIITRI R2 he e R1 n R2 ha th a u given ab e with a phydr'oxyetho xybenaaldehyde selected from those represented by the following general formula: (V11) 0 i J-1r H O-OII2CH2-O The condensations can advantageously be carried out in the presence of an acid condensing agent, such as glacial acetic acid, etc. While the reaction mixture can be heated, there is generally no advantage in doing so due to the exothermic nature of the reaction. The intermediates represented by Formula II above can advantageously be prepared by heating together a compound selected from those represented by the following general formula:

(VIII) 3 no I wherein R has the values given above with ethylenechlorohydrin. Such a reaction, using hydroxy aromatic aldehydes instead of a benzophenone compound, is shown I by Bernstein et al.-Jour. Amer. Chem. Soc. vol 73 page 90 6.. For example, by reacting ethylenehrd n to ethe i -b ZI Y hYdPPKY- teasers. than abate answer-se re a- I ethoxybenzophenone having a melting point of 9()--92 C.

On analysis, this compound contained C, 69.5% and H, 5.8%, whereas the calculated values are C, 69.6% and H, 5.5%.

The compounds selected from those represented by Formula III above can advantageously be prepared according to the method described in Sawdey U. S. application Sei'. no. 419,239, filed March 2.9, 1954 (now U. S. Patent 2,739,888, issued March 27, 1956), i. e., by reacting a compound corresponding to that of Formula III above, except that a methylene group is present in the 5-position, with an aromatic aldehyde, such as P-B- hydroxyethoxybenzaldehyde.

The compounds of Formula IV above can advantageously be prepared by condensing a compound selected from those represented by Formula VI above with an aromatic aldehyde containing a primary amino group, such as p-aminobenzaldehyde.

The compounds selected from those represented by Formula V above can advantageously be prepared by condensing the compound having the following formula:

(IX) O =CNC2H4-NH5 H20 =O with an aldehyde represented by the following general formulai t-ii-H wherein R has the values given above. Alternatively,

' the polymeric ultraviolet absorbing compounds of my invention comprising an amide of a compound represented by Formula V above can be prepared by first e0ndensing the compound of Formula IX with one of the polymerized monoethylenically-unsaturated' compounds of my invention, followed by condensation of this product with an aldehyde represented by Formula X above.

Figure l of the accompanying drawing illustrates schematically 'a cross-sectional view of a sensitive photographic element having an ultraviolet filter layer contaim ing one of the compounds of my invention. These intraviolet absorbing compounds can be incorporated in the photographic element in a variety of ways, depending on the ultimate use of the photographic element and the degree of protection desired. Advantageously, the ultraviolet absorbing compound can be dissolved or dispersed in a solvent medium together with a colloidalbinder, such as gelatin, cellulose esters (e. g., cellulose acetate, etc.), synthetic resins (e. g., polyvinyl acetal s, hydrolyzed polyvinyl acetate, etc.), etc., and the resulting mixture coated over the light-sensitive layer of the photographic element. Where the photographic element is a material intended for use in color photography, the ultraviolet filter layer need not be an outer layer, but this layer can be placed over one of the layers subject to the harmful effects of ultraviolet radiation. For example, in a multilayer material comprising three differentially sensitized; layers, the red sensitive layer being adjacent to the support, the green sensitive layer being superposed on the red sensi tive layer, and the blue sensitive layer being outermost with respect to the other light-sensitive layers, theultraviolet filter layer can be placed between the blue andgreen sensitive layers. Alternatively, the ultraviolet filter layer can be placed between the green and the red sensitive layers. If desired, the material useful in absorbing the ultraviolet radiation can be incorporated directly i n the light-sensitive emulsion instead of, or in"addition to, being present in another layer. The amount of ultraviolet absorbing compound used can be varied, depending upon the effect desired and the use to whichthe materialis to be put.

The support ofv the photographic element can be transparent, such as a cellulose ester (cellulose acetate, etcl) support. Other supports such 135 6? C. -Analysis.-N, found: 10.2 hydroxyethoxybenzaldehyde Reaction with "stirring ona steam bathfo r 2% hours. distilled water were then added and heating was con- .with ether in a Soxhlet apparatus.

as Iglass, metal, etc., can

be employed, if desired. H EXAMPLE A.STYRENE-MALEIC ANHYDRIDE INTERPOLYMER AND p-B-HYDROXYETHOXY- BENZALDEHYDE a METHYL a PHENYL- HYDRAZONE T he preparation of the ot-methyl-u-phenylhydr p-fi hydr0xyeth0xybenzaldehyde 'drazine, followed by 105 ml. of glacial acetic acid.

Some heat was spontaneously evolved and the reaction solution set to a mass of crystals. After 15 minutes at room temperature the mass was diluted with water and the crystals were filtered onto a Biichner funnel. The product wasrecrystallized from absolute ethyl alcohol with treatment by decolorizing carbon (Norite). The yield was 31 g. of very light yellow crystals melting at percent; calculated for p-fla methyl a phenylhydrazone (C H O N ):10.37 percent.

styrene-maleic anhydride interpolymer [.In an all-glass outfit, equipped with a reflux condenser and calcium chloride tube and a mechanical stirrer, g. of styrene-maleic anhydrideinterpolymer were dispersed in 80 ml. of dry pyridine. To this dope were added g.

of l ot-methyl-a-phenylhydrazone of p fi-hydroxyethoxybenzaldehyde, and the reaction mixturewas heated with Ten ml. of

tinued for an additional one-half hour. After cooling, the dope was poured in a fine stream into 2 liters of stirred ether, and the friable precipitate was washed in a beaker with 1 liter offresh ether and then extracted The product was dried in a vacuum desiccator; yield 17.5 g.; N= 3.8 percent.

Thelight-colored product did not appear to be direct- "ly soluble in dilute ammonium or sodium hydroxide,

but'itwas dissolved 'in wet acetone to-yield a moderately concentrated dope which turned turbid on addition of more water. At this stage, the addition of a small amount "of dilute base cleared the solution, which could then be infinitely diluted'with water without precipitation.

InTable "Iare listed the polymers containing anhydride groups which were reacted withhydroxyl-bearing sim'ple organic ultraviolet absorbent by the above procedure to yield polymeric non-difiusing ultraviolet absorbers.

ULTRAVILOET ABSORBER (1) Preparation of pamino!)enzaldehyde-a-methyl-uphenylhydrazone In an all-glass reflux outfit, 30.0 g. of p-nitrobenzaldehyde were dissolved on a steam bath in 200 ml. of absolute ethyl alcohol. To the solution were added 27.0 g. ofa-methyl-a-phenylhydrazine and the heating was continued. In a short while the reaction mixture set to a mass of crystals. Two hundred ml. more of absolute ethyl alcohol were added and heating was continued for a total time of 30 minutes. The solution containing some undissolved crystals was chilled. The crystals were filtered oif, recrystallizedfrom absolute ethyl alcohol, and dried. The yield was 47 g-., melting point 134-5" C.

The above nitro derivative was reduced by an adaptation of the procedure of Borsche and Sell for anils [Ber., 83, 86 (1950)]. Twelve g. were suspended in 300 ml. of boiling absolute ethyl alcohol and a hot solution of sodium sulfide in 200ml. of 1:1 ethyl alcoholzdistilled water was added slowly. The color of the reaction mixture changed from orange to brown to yellow. After all the sodium sulfide solution had been added, the solution was boiled for two minutes and then crystallization was induced by adding water to incipient turbidity and chilling. The crystals were filtered onto a. Biichner funnel, redissolved in a minimum amount of boiling alcohol and the solution was filtered by suction through paper and a layer of filter aid. Crystallization was again induced by addition of water to the boiling solution to incipient turbidity and chilling. The product was filtered onto a Biichner funnel, washed with water on the funnel, and dried in a vacuum desiccator over calcium chloride under a constantly applied water pump vacuum. Seven and one-half g. of light buif crystals, which melted at 1323 C., were obtained.

Analysis-Found: C, 74.5 percent; H, 6.5 percent; N, 18.4 percent. Calculated for p-aminobenzaldehydeot-methyl-a-phenylhydrazone (C H N C, 74.7 percent; H, 6.7 percent; N, 18.7 percent.

(2) Reaction of poly-acrylic anhydride and p-aminobenzaldehydc-a-methyl-a-phenylhydrazone 1 'rABLE rQ-REA TION 0F POLYMER WITH HYDROXY-CONTAINING ORGANIC "then quickly dried in the air.

ing conthmed :for another hour. The dope was cooled,

a fine stream into 1 liter of stirred ether. The friable precipitate was stirred with 500 ml. of fresh ether and It was suspended in 50 ml. of acetone and water was slowly added to effect solution. The dope was then poured into 1 /2 liter of distilled water containing 125 ml. of concentrated bydrochloric acid, with stirring. The precipitate was extracted with two SOO-ml. portions of fresh water by mechanically stirring for 30 minutes and filtering after each. The product Was dried in a vacuum desiccator over calcium chloride under a constantly applied water pump vacuum. The yield was 6 g. The nitrogen content of the product was 10.5 percent.

EXAMPLE 'J.POLYACRYLIC ANHYDRIDE AND 3 [3 AMI-NOETHYL-S-BENZALTHIAZOLIDINE- DIONE-2,4

Te'n .g. of acrylic anhydride and g. of 3-;8-aminoethyl-5-benzalthiazolidinedione-2,4 hydrochloride was re- In an all-glass outfit, equipped with a reflux condenser with calcium chloride tube and a mechanical stirrer, were placed 7 g. of polyacrylic 'anhydride, 9g. of 3-aminoethylthiazolidinedione-2,4, and -70 ml. of dry pyridine.

The reaction was heated on a steam bath for two hours, and 3.5 ml. of distilled water were added. After minutes of additional heating, the dope was cooled and poured into 3 liters of ether. The soft precipitate was extracted with fresh ether and redissolved on a steam bath in 90 ml. of acetone with sufiicient water added to effect solution. The dope was poured into 1 /2 liters of distilled water containing 10ml. 'of concentrated hydrochloric acid and the soft precipitate obtained was kneaded repeatedly with fresh l-liter portions of distilled water until free from acid. The'product-was dried in a vacuum desiccator over calcium chloride under a constantly applied water pump vacuum. The yield was 8 g.

(2) Reaction with anisaldehyde Six g. of the reaction product from Example 'K-l above, 30 ml. of glacial acetic acid and ml. of anisaldehyde were stirred on a steam bath until a smooth dope was obtained. The reaction mixture was then heated on a steam bath for 1% hours. The dope, after cooling, was poured into 1% liters of ether and the friable precipitate was thoroughly extracted with ether. The product was dried under a constantly applied water pump vacuum. The yield was 8 g.

Analysis.N, 7.1; S, 8.3.

The m-;3-hydroxyethoxybenzaldehyde' used in Example E above was prepared according to the method described by Bernstein et al., ibid., using 'rn-'hydroxybenzaldehyde in place of p-hydroxybenzaldehyde. It had a boiling point of 143.8 C. at 0.4 mm.

The following examples describe the preparation of a photographic coating from certain of the new polymeric ultraviolet absorbing compounds -:of my invention.

Example 1.l.0 g. of the polymeric compound ob- 8 tained as described inExample A above was wetted with 1 cc. of acetone and 5 drops of 28% ammonium hy droxide. 20.0 cc. of water was added and solution was elfec't'ed by gentle warming and this solution was then added to 20 cc. of warm 10% aqueous gelatin solution.

The solution was then coated on a'transparent support and the absorption of the coating measured 'in-the usual manner. The curve obtained .is shown in Fig. 2 of the drawing and is represented by line A. The coating was then subjected to a conventional alkaline photographic developer and the absorption of the .coating measured once again. The absorption of the coating thus treated is represented by curve B in Fig. 2 {dotted line). Thus, the ;.polymeric ultraviolet compounds of my invention undergo no substantial change .dueto treatment inphotographic developing solutions. Asecond coating was .pr'epared substantially in the :manner shown above, and this coating subjected .to-exposure in an east window for one week. At the end of that time, the coatinghad substantially the same absorption characteristics as shown in curve A of Fig. 2.

Example 2.-1.0 g. of the polymeric compoundobtained as described in Example F above was wetted with 1 cc. of acetone and 5 drops of 28% ammonium hydroxide. 20.0 cc. of water was added and solution was effected by gentle warming and tln's solution was :then added to 20 cc. of warm 10% aqueous gelatin solution.

This solution was then coated on a'transparent support,

.the ultraviolet compound has been substantially unchanged by treatmentin a photographic developing solution. Also, a second coating was prepared as in Example I above and this coating subjected to exposure for .one week in an-east window. The absorption characteristics of the coating had undergone substantially no change iand the curve was substantially identical to line C of Other polymeric ultraviolet absorbing compounds obtained according to myinvention exhibit similar absorption characteristics to the compounds shownin Examples 1 and 2'above.

In the accompanying drawings, Fig. 1 illustrates schematically a cross-sectional view of a photographic element containing -a .layer having incorporated therein a polymeric ultraviolet absorbing compound obtained according to my invention. As shown in Fig. .1, a support 10'of any suitable material, such as cellulose acetate, or paper, having thereon an emulsion layer 11 is coated with a filter layer 12 having incorporated therein a polymeric ultraviolet absorbing compound obtained according to my invention, such as is described in Example C above. It will be understood that Fig. 1 of the drawing is merely representative of other structures which can be employed in my invention and that the element can have other layers, not shown, as additional lightsensitive layers, subbing layers, anti-halation layers, etc.

By the term hydroxyalkyl as used herein, l mean.such a group as HOCH CH which might be attached directly 'to an aryl group, or HOCH CH O which contains theHOCH CH group and is attached to an aryl -groupthrough an oxygen atom (or other linkage, such as sulfur).

Ihave'found that the esterification or amide formation characteristic of my invention occurs at the alcoholic hydroxyl (and not at aphenolic hydroxyl) or primary amino group, respectively. Esterification at a phenolic hydroxide'would affect the absorption characteristics of the compounds represented by Formulas I-III above,

precipitate was filtered madame. 1

- w men p-p-Hydroxyethylaniline (34 g;) in 100 ml. of benzene was treated with 29 mi -of phenyl mustard oil A vigorous reaction ensued. Afterco oling, the crystalline H a a a off and theproduct recrystallized from alcohol to yield'46 g. of 'thethiourea. M. P. 138- 140 C.

EXAMPLE M.3-(p-,3-HYDROXYETHYLPHENYL) Z-PHENYLIMINO THIAZOLIDINE a CaHsN B A mixture of the above urea (46 g.), chloroacetate, and 18 ml. of pyridine in 150 ml. of ethanol was refluxed for 5 hours. On cooling the product separated as an oil. The alcohol was decanted and the crude thiazolidone, 32 g., used in the next step.

EXAMPLE N.5 BENZAL 3 (p fi HYDROXY- ETHYLPHENYL)-2-PHENYLIMINO THIAZOLI- DONE The thiazolidone (32 g.), ml. of benzaldehyde and 10 ml. of piperidine in 180 ml. of methanol were refluxed for 3 hours, then chilled. The product which separated was filtered oif and recrystallized from alcohol to give 37 g. of the benzal derivative. M. P. l09-1l0 C.

What I claim as my invention and desire secured by Letters Patent of the United States is:

l. A photographic element comprising a support, at least one photographic silver halide emulsion layer and incorporated in one of the layers of said photographic element an ester of a compound selected from the group consisting of those represented by the following three general formulas:

22 ml. of ethyl wherein R and R each represents a member selected from the group consisting of an alkyl group and an aryl group, R,, R, and R each represents an aryl group, and R represents a member selected from the group consisting of an alkyl group and an aryl group, provided that at least one of the groups selected from the group consisting of R and R contains a hydroxyalkyl radical containing from 2 to 3 carbon atoms, the hydroxyl group of the hydroxyalkyl group of said compound selected from the group consisting 10 a t a of (a), (b), and (0) having been esterified by a polymerized monoethylenically-unsaturated compound containing reactive groups selected from the group consisting of carboxylic' halide and carboxylic anhydride groups.

2. A photographic element comprising a support, at least one photographic gelatino-silver-halide emulsion layer, and incorporated in one of the layers of said photographic element an ester of a compound selected from those represented by the following general formula:

HO-CzHr-O R1 wherein R and R each represents a member selected from the group consisting of an alkyl group containing from 1 to 2 carbon atoms and a monocyclic aryl group of the benzene series, said compound having been esterified by a polymerized monoethylenically-unsaturated compound containing a group selected from the group consisting of carboxylic halide and carboxylic anhydride groups.

4. A photographic element as defined in claim 3 wherein said polymerized monoethylenically-unsaturated compound is a styrene-maleic anhydride interpolymer.

5. A photographic element comprising a support, at least one photographic gelatino-silver-halide emulsion layer superposed on said support, and an outer gelatin layer containing an ester of a styrene-maleic anhydride interpolymer and p-;8-hydroxyethoxybenzaldehyde-ozmethyl-ot-phenylhydrazone.

6. A photographic element comprising a support, at least one photographic gelatino-silver-halide emulsion layer, and incorporated in one of the layers of said photographic element an ester of a compound selected from those represented by the following general formula:

I HO-CaH 0 wherein R represents an aryl group, said compound having been esterified by a polymerized monoethylenically-unsaturated compound containing a group selected from the group consisting of carboxylic halide and carboxylic anhydride groups.

7. A photographic element comprising a support, at least one photographic gelatino-silver-halide emulsion layer, and incorporated in one of the layers of said photographic element an ester of a compound selected from those represented by the following general formula:

wherein R represents a monocyclic aryl group of the benzene series, said compound having been esterified by a polymerized monoethylenically-unsaturated compound containing a group selected from the group consisting of carboxylic halide and carboxylic anhydride groups.

11 ,8. A photographic element comprising a support, at least one photographic gelatino silver-halide emulsion layer superposed on said support, and an outer gelatin :layer containing an ester of a styrene-ma'leic anhydride interpolymer and 2-hydroxy-4-B hydroxyethoxybenz0- phenone.

.9. A photographic element comprising a support, at least one photographic gelatino-silver-halide emulsion layer, and incorporated in one of the layers of said photographic element an ester of a compound selected "from those represented by the following general formula:

0=C|3-NR Ra-CH=C O=N-R5 8 wherein' R' and R each represents .an aryl group, and R represents amember selected from the group cons'isting-of :an =alkyl group and an aryl group, provided that at least one of the groups selected from the group consisting of R and R contains a hydroxyalkyl radical containing *from to '3 carbon atoms, :said compound having been esterifiedby a polymerized monoethylerfically-um saturated "compound containing a group selected from the group consisting of carboxylic halide and carboxylic anhydride groups.

10. A photographic element comprising a support, at least one photographic gelat'ino-silver-halide emulsion layer superposed on said support, and an outer gelatin layer containing an ester 'ofpolyacrylic anhydride and 3 ethyl 5 p 1(5 hydroxyethoxy'wenzal 2 phenylimino-4-thiazolidone.

References Cited in the file of this patent 'ST- ATES' PATENTS 2,357,393 Frohlich et a1. Sept. 5 1944 '2;691 ;579 Fierke r Oct. 12, $1954 2,,7-395888- 'Sawdey "Mar. '27, 195.6 

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT, AT LEAST ONE PHOTOGRAPHIC SILVER HILIDE EMULSION LAYER AND INCORPORATED IN ONE OF THE LAYERS OF SAID PHOTOGRAPHIC ELEMENT AN ESTER OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THOSE REPRESENTED BY THE FOLLOWING THREE GENERAL FORMULAS: 